Production of amino alcohol derivatives



n r S8 fiemrenfipg Search ROOm Patented Jan. 12, 1937 i UNITED STATES PATENT OFFlCE PRODUCTION OF AIVDNO ALCOHOL DERIVATIVES Henry Dreyfus, London, England No Drawing. Application August 22, 1932, Serial 21321629398. In Great Britain September 18,

10 Claims. (Cl. 260-9912) This invention relates to the manufacture of products obtained from aliphatic di-carboxylic new organic compounds which are particularly acids, e. g. sebacic acid, by condensation with of value as sizing, wetting, cleansing or deteralcohols, and in addition the purely synthetic gent, dispersing, and emulsifying agents in the acid resins containing a free carboxy group, for treatment of substances or materials-in general, example the products obtained by condensation and also in the treatment 01' textiles and fibres of salicyclic acid or other phenol carboxylic in general, for which purpose the new compounds acids with formaldehyde or other aldehydes. are also of value as de-electrifiers, wetting agents The products produced as above may be conand detergents. verted by sulphonation into substances which According to the present invention, the new have a still stronger dispersing action or wetting 10 organic compounds are prepared by combining action upon solids and upon textile materials. resin acids or naphthenicacids with amino alco- Such sulphonation may be efiected either after, hols. The compounds may be of the type of during or before combination of the naphthenic simple addition products in which the amino or resin acids with the amino alcohols. In fact alcohol adds itself to the resin or naphthenic the invention envisages the combination or con- 5 acid, or of the type of condensation product prodensation of an already sulphonated amino alcoduced by the combination of the acid with either hol with a resin or naphthenic acid or of an althe amino group or the alcoholic group of the ready sulphonated resin or naphthenic acid with aminoalcohol or both, with elimination of water. an amino alcohol. It is preferable, however, to Furthermore, the products obtained by acidylaefi'ect the sulphonation simultaneously with or 20 tion of the amino group with the resin or naphafter the combination of the resin or naphthenic thenic acid radicle may have the free alcoholic acid with the amino alcohol. The sulphonation group substituted, as for example by another acid may be effected by simple treatment with strong radicle. sulphuric acid, or with chlor-sulphonic acid or As amino alcohols for use according to the with sulphur trloxide, of the compounds of the 25 present invention I may mention mono-, diand resin or naphthenic acid with the amino alcotri-ethanolamine, and the commercial product hol or one or more of the reagents taking part known as ethanolamine which is a mixture of in the combination. The stronger sulphonating two or even three of the ethanolamines, propanolagents such as ehlor-sulphonic acid and sulphur min i m n pr p n l, ixy-p p n mine, trioxide have the advantage that they can pro- 30 butanolamine, pentanolamine and bodies simiduce more highly sulphonated products. The lar to the diand tri-ethanolamines wherein more sulphonation products manufactured according than One hy atom of the parent n a to the present invention, and particularly the is substituted by a higher oxy-alkyl group, and highly sulphonated products, are even more also compounds in which one or two hydrogen stable towards hard water than are the simple 35 atoms of the-parent ammonia is or are subunsulphonated products. stituted by an oxy-alkyl group, and one or two The combination of the amino alcohol with of the remaining hydrogen atoms by a group of the resin or naphthenic acid may be brought a different type, as for example a simple alkyl about by simple mixing of the compounds, but group, or an w-amino-alkyl group. Such. bodies is preferably facilitated by heating the com- 40 may be made for instance by the action of pounds, especially when it is desired to produce ethylene oxide upon ethylene diamine. As the a condensation either with the amino group or resin and naphthenic acids for combinining with the alcohol group or both of the amino alcohol. the ami o alcohols I m mention l t e Further, condensation-may be much facilitated naphthenic acids, and Particularly the flp by employing a condensing agent, as for example 45 thenic acids which can be extracted or prepared sulphuric acid or phosphoric acid. As already from Baku petroleum and the resin' acids of indicated sulphuric acid may be employed to colophony, Congo copal, kauri copal, Manila bring about a simultaneous sulphonation of the copal and Zanbizar copal; In addition the presproduct. ent invention further includes the use of the When the acid is a. dior poly-carboxylic acid, 50 synthetic resin acids, for example those obtained as in the case of most of the naphthenie acids, by condensation of natural resins with phenol and in the case of some of the synthetic resin aldehyde condensation products and with other acids, as for example the condensation products synthetic resin products, as for example the of salicylic and like acids with formaldehyde, the 56 glyptal and urea synthetic products and the amino alcohol may be caused to combine with f COMPOSITIONSI all or only part of the carboxy groups. This may be brought about by suitable adjustment of the proportions of the reagents. When only part of the carboxy groups are reacted or closed by means. of the amino alcohols, the remaining carboxy group or groups may be converted into salts. as for example with caustic soda or potash or ammonia, or into further esters as desired.

Instead of combining the amino alcohol directly with a synthetic acid resin as described above, the amino alcohol may first be combined with one of the reagents used to produce the resin, and the product then reacted with the other reagent or reagents to produce directly the amino alcohol compound of the resin acid. Thus for instance an amino alcohol, for example monoor diethanolamine, may be caused to react with salicylic acid or other aromatic oxy-carboxylic acid, and the product then treated with formaldehyde, furfural or other suitable agent for forming a resin with salicylic acid.

For de-electrifying and similar purposes the compounds of the present invention may conveniently be applied in solution in suitable mineral oils, and their formation may actually take place in this medium, the amino alcohols and resin or naphthenic acids being added in suitable proportions and then caused to react. Some.

oils, particularly those of Russian origin, have a natural content of naphthenic acids, and when these are used it may be unnecessary to add more acids, and the proportion may even be reduced by the addition of acid-free oils or other liquids.

Furthermore the combination or condensation of one resin-forming reagent with the amino alcohol may be brought about simultaneously with the resin-forming reaction itself.

As previously indicated the new products are especially of value as sizing, wetting, cleansing, emulsifying and dispersing agents, and as deelectrifiers in the arts. Some of the products lend themselves more particularly to one purpose, and other products to other purposes. For instance, the products obtained by condensation of an amino alcohol with part of the carboxy groups of a dior poly-carboxylic naphthenic or resin acid and also the salts of such products have more powerful emulsifying or dispersing properties than the products in which all carboxy groups are reacted, and similarly all the sulphonation products of the present invention are highly valuable as emulsifying and dispersing agents. All the products are useful as wetting and cleansing agents. As regards de-electrifying properties the products which are of greatest value are the simple addition products of the amino alcohols with the resin and naphthenic acids, and also the condensation products in which the amino. group is reacted with the naphthenic or resin acid.

The products, and especially those containing free amino groups, are also of value as agents for preventing acid fading of dyestuffs on textile materials and particularly on textile or other materials made of or containing cellulose acetate or other organic derivative of cellulose which have been coloured or are to be coloured with aminoor alkyl-amino-anthraquinones.

The products are further useful as lubricants, and especially those products which act as good de-electrifiers. Thus the products may be used as lubricants for textiles in weaving, knitting, winding or winding and twisting generally, and especially winding or winding and twisting of artificial filaments, for example continuously with their production either by dry or wet spinning Cross Reference lubricants, which are liable to oxidation to acidic products, and hence in this application'may be said to prevent acid fading of dyestuffs by removing the cause thereof. For de-electrifiers and lubricants, the bodies may be employed together with diethylene glycol, glycerine or other di'- or poly-hydric alcohols.

As wetting agents the products of-the invention are of greatest value in the wetting of solids so as to form pastes, for example in printing pastes and in commercial pastes containing vat and other insoluble dyes which have subsequently to be converted into solutions or dispersions. In the textile industries the products are of value in any wet treatment of textiles, as for example in mercerizing of cotton and other cellulosic fibres, dyeing or fibres of all kinds, the fulling of wool, the carbonizing of cotton and cellulosic fibres, and the killing of skins. As wetting agents the new substances are further of importance in the crepe twisting of artificial and other filaments or yarns in order to produce crepe fabrics. It is of great assistance in crpe twisting to apply water or other wetting substance before or during twisting or between stages of the twisting. The products of the present invention facilitate such wetting. Furthermore in the manufacture of staple fibre, using for instance artificial filaments. and especially filaments of cellulose acetate orother cellulose derivatives, it is of advantage to cut a compact bundle of filaments which has been wetted with water. Such wetting may again be facilitated by the wetting agents of the present invention.

As dispersing agents the products are particularly of value in the conversion of water-insoluble dyestuffs into dispersion for use in dyeing, printing and stenciling of textile fibres, and in particular fibres of cellulose acetate or other organic derivatives of cellulose for which the waterinsoluble dyestuffs are to-day of most value. The products may also be used for the purpose of dispersing lakes, insoluble pigments and pigment dyestuffs intoqiuitable dispersions for use lose and also in the treatment of films, sheets andthe like of esters or of ethers of cellulose or other materials which are liable to electrification. In the case of the artificial filaments or other materials such as those made of cellulose derivatives the de-electrifiers of the present invention may be applied to the materials after manufacture or dissolved or dispersed in the solutions used in the manufacture of the materials.

The products obtained according to the present invention are also of value in the sizing both of natural textile fibres and also of artificial fibres having a cellulosic base, such as those obtained by the viscose, cuprammonium or nitro-cellulose processes, and those having a base of an organic derivative of cellulose, for example, cellulose acetate.

While in the above description particular examples have been given of application of the new search Room acaznwe substances, it is to be understood that the invention includes their use generally in the arts.

The following examples illustrate the invention but it is to be understood that they do not limit it in any way:-

Example 1 Equivalent quantities of mono-ethanolarnine and abietic acid are heated together at from 90-100 C. for about 30 minutes and a darkcoloured liquid product ls obtained, which solidifies on cooling-and is very suitable for use as a size when dissolved in an appropriate solvent, e. g. xylene.

If desired, tri-ethanolamine may be substituted for the mono-ethanolamine used in the above example, and a similar product is obtained.

Example 2 Example 3 The following example shows the use of the products obtained according to the present invention in the sizing of textiles.

'A solution'in xylene of from 30-50% concen-- tration of the :compound obtained according to Example 1 is prepared and applied to a cellulose acetate yarn by contacting the yarn during its transfer from one supporting device to another with a roller dipping into the xylene solution.

The size may also be applied by immersion methods, but in this case a weaker solution, e. g. %-25% is preferably used.

Example 4 The following example shows the use oi. the products obtained according to the present invention in the dyeing of textiles with waterinsoluble dyestuffs.

A blue violet shade may be obtained upon a cellulose acetate woven fabric in the following manner. A dyebath is prepared by grinding together about 4 lbs. of the product obtained by reacting naphthenlc acid with ethanolamine in the presence of sulphuric acid and 1 lb. of 1- amino 4 methylamino anthraquinone, stirring the mixture into 10 gallons of boiling water and straining the dispersion into 360 gallons of water in a suitable dyeing machine. 100 lbs. of fabric are then entered at -30 the temperature raised during minutes to 75 C. and the goods worked at this temperature for 1 hour. They are then removed, washed and dried.

What I claim and desire to secure by Letters Patent is:-

1. Process for the production of organic com pounds which comprises condensing an amino alcohol with an acid selected from the group consisting of synthetic resin acids and naphthenic acids.

2. Process for the production of organic compounds which comprises condensing an alkylolamine with an acid selected from the group consisting of synthetic resin acids and naphthenic acids.

3. Process for the production of organic compounds which comprises condensing an. ethanolamine with an acid selected from the group consisting of synthetic resin acids and naphthenic acids.

4. Process for the production of organic compounds which comprises condensing an amino alcohol with a synthetic resin acid.

5. Process for the production of sulphonated organic compounds which comprises condensing an amino alcohol with an acid selected from the group consisting fof resin acids and naphthenic acids and sulphonating the product.

6. Process for the production of sulphonated organic compounds which comprises condensing an ethanolamine with. anacidselected from the group consisting Tot resin acids and naphthenic acids and sulphonating the product.

7. Process for the production of sulphonated organic compounds which comprises condensing an amino alcohol with an acid selected from the group consisting of resin acids and naphthenic acids in the presence of a sulphonating. agent.

8. Process for the production of sulphonated organic compounds which comprises condensing an alkylolamine with an acid selectedfrom the group consisting of resin acids and naphthenic acids in the presence of a sulphonating agent.

9. Sulphonated condensation products of amino alcohols with acids selected from the group consisting of resin acids and naphthenic acids.

10. Sulphonated condensation products of a1- kylolamines with acids selected from the group consisting of resin acids and naphthenic acids.

HENRY DREYFUS. 

